Spectrally sensitized silver halide photographic emulsions

ABSTRACT

A SILVER HALIDE PHOTOGRAPHIC EMULSION SPECTRALLY SENSITIZED WITH A COMBINATION OF AT LEAST ONE MONOMETHINE CYANINE DYE REPRESENTED BY GENERAL FORMULA 1   1-R1,2-((-N(-R2)-Z1-)&gt;C=CH-),R3-QUINOLINIUM (X1(-))(P-1)   WHEREIN R6 AND R7 EACH REPRESENT A MEMBER SELECTED FROM THE GROUP CONSISTING OF A Y-SULFPROPYL GROUP, A YSULFOBUTYL GROUP, A $-SULFOBUTYL GROUP, A $-CARBOXYBUTYL GROUP, AND AN W-CARBOXYPENTYL GROUP; R6 REPRESENTS A MEMBER SELECTED FROM THE GROUP CONSISTING OF METHYL GROUP AND AN ETHYL GROUP; Y3 AND Y4 EACH REPRESENT A MEMBER SELECTED FROM THE GROUP CONSISTING OF A SULFUR ATOM AND SELENIUM ATOM; V1 AND V2 EACH REPRESENT A MEMBER SELECTED FROM THE GROUP CONSISTING OF A HYDROGEN ATOM AND A HALOGEN ATOM; X3 - REPRESENTS AN ACID ANION; AND R IS AN INTEGER OF 1 OR 2, SAID R BEING 1 WHEN THE DYE TAKES A BETAINE STRUCTURE.   N(-R7)-(5-V2-1,2-PHENYLENE)-Y4-))-) (X3(-))(R-1)   Y3&lt;(-(4-V1-1,2-PHENYLENE)-N(+)(-R6)=C(-CH=C(-R8)-CH=C&lt;(-   WHEREIN R4 REPRESENTS A MEMBER SELECTED FROM THE GROUP CONSISTING OF AN ETHYL GROUP, AN N-PROPYL GROUP, AN N-BUTYL GROUP, AND AN ALLYL GROUP; R5 REPRESENTS A MEMBER SELECTED FROM THE GROUP CONSISTING OF A Y-SULFOPROPYL GROUP, A Y-SULFOBUTYL GROUP, A $-SULFOBUTYL GROUP, A $CARBOXYBUTYL GROUP, AND AN W-CARBOXYPENTYL GROUP; Y, A $-CARBOXYREPRESENT A MEMBER SELECTED FROM THE GROUP CONSISTING OF A SULFUR ATOM AND A SELENIUM ATOM; X2 REPRESENTS AN ACID ANION; AND Q IS AN INTEGER OF 1 OR 2, SAID Q IS 1 WHEN THE DYE TAKES A BETAINE STRUCTURE, AND AT LEAST ONE CARBOCYANINE DYE REPRESENTED BY GENERAL FORMULA 111   (1,2-PHENYLENE)-N(-R5)-))-) (X2(-))(Q-1)   Y1&lt;(-(1,2-PHENYLENE)-N(+)(-R4)=C(-CH=C(-CH3)-CH=C&lt;(-Y2-   WHEREIN R1 AND R2 EACH REPRESENT A MEMBER SELECTED FROM THE GROUP CONSISTING OF AN ALKYL GROUP, A SUBSTITUTED ALKYL GROUP AND AN ALLYL GROUP; R3 REPRESENTS A MEMBER SELECTED FROM THE GROUP CONSISTING OF A HYDROGEN ATOM AND A METHYL GROUP; Z1 REPRESENTS AN ATOMIC GROUP NECESSARY TO COMPLETE A MEMBER SELECTED FROM THE GROUP CONSISTING OF A 2-QUINOLINE NUCLUES, A BENZOTHIAZOLE NUCLEUS, A BENZOSELENAZOLE NUCLEUS, AND A NAPHTHOTHIAZOLE NUCLEUS, THE HYDROGEN ATOM OF SAID NUCLEUS CAPABLE OF BEING SUBSTITUTED ALKYL; X1- REPRESENTS AN ACID ANION; AND P IS AN INTEGER OF 1 OR 2; SAID P BEING 1 WHEN SAID R1 OR R2 IS A SUBSTITUTED ALKYL GROUP AND THE DYE TAKES A BETAINE STRUCTURE; AT LEAST ONE OF THE CARBOCYANINE DYES REPRESENTED BY GENERAL FORMULA 11

United States Patent ABSTRACT 6F THE DISCLOSURE A silver halide photographic emulsion spectrally sensitized with a combination of at least one monomethine cyanine dye represented by General Formula I GENERAL FORMULA I CH: ii i,

wherein R and R each represent a member selected from the group consisting of an alkyl group, a substituted alkyl group and an allyl group; R represents a member selected from the group consisting of a hydrogen atom and a methyl group; Z represents an atomic group necessary to complete a member selected from the group consisting of a 2-qulnoline nucleus, a benzothiazole nucleus, a benzoselenazole nucleus, and a naphthothiazole nucleus, the hydrogen atom of said nucleus capable of being substituted; X represents an acid anion; and p is an integer of l or 2; said p being 1 when said R or R is a substituted alkyl group and the dye takes a betaine structure; at least one of the carbocyanine dyes represented by General Formula 11 GENERAL FORMULA II wherein R represents a member selected from the group consisting of an ethyl group, an n-propyl group, an n-butyl group, and an allyl group; R represents a member selected from the group consisting of a y-sulfopmpyl group, a -sulfobutyl group, a 6-sulfobutyl group, a B-carboxybutyl group, and an w-carboxypentyl group; Y and Y represent a member selected from the group consisting of a sulfur atom and a selenium atom; X represents an acid anion; and q is an integer of 1 or 2, said q is 1 when the dye takes a betaine structure, and at least one carbocyanine dye represented by General Formula III GENERAL FORMULA III wherein R and R each represent a member selected from the group consisting of a -sulfpropyl group, a 'ysulfobutyl group, a fi-sulfobutyl group, a fi-carboxybutyl group, and an w-carboxypentyl group; R represents a member selected from the group consisting of a methyl 3,7415,i45 Patented July 110, 1973 BACKGROUND OF THE INVENTION 1) Field of the invention The present invention is directed to a spectrally sensitized silver halide photographic emulsion and more particularly to a photographic emulsion sensitized uniformly orthopanchromatically over a visible region of from 380 nm. to 650 nm.*

(2) Description of the prior art For producing a photographic emulsion having a uniformly high sensitivity over a visible region of from 380 nm. to 650 nm., which is one of the objects of this invention, two or more sensitizing dyes are frequently used in combination. In this case, the sensitivity obtained by using a combination of two or more sensitizing dyes is lower than the sensitivity obtained by employing each sensitizing dye alone. However, when a combination of specifically selected dyes is employed, a super-additively higher sensitivity is obtained. The eilect of a combination of dyes in such a manner is known as supersensitization and it is one of the objects of this invention to discover such an efiective combination.

It is particularly known that a green sensitivity distribution over 560-5 run. and a red sensitivity distribution over 630-650 nrn. provide important influences on the improvement in the tone reproduction for unexposed light-sensitive photographic films sensitized orthopanchromatically. Among them, it is desirable that the red sensitivity distribution has a maximum spectral sensitivity at 635 nm. and also a gently inclining spectral sensitivity up to amount 650 nm.

Another object of this invention is to obtain a spectral sensitivity having a gentle sensitivity distribution up to about 650 nm. without reducing the maximum sensitivity at 630640 nm., while maintaining a high white-light sensitivity of a silver halide photographic emulsion.

SUMMARY OF THE INVENTION The objects of this invention can be achieved by incorporating a combination of at least one monomethine cyanine dye as shown by the following General Formula I, at least one carbocyanine dye as shown by the following General Formula II and at least one carbocyanine dye as shown by the following general Formula III in a silver halide photographic emulsion:

GENERAL FORMULA I wherein R and R each represent an alkyl group (such as methyl group, an ethyl group, a propyl group and the like), a substituted alkyl group (such as an acetoxyalkyl group (e.g. an acetoxypropyl group), a sulio alkyl group (e.g. a B-sulfobutyl group) a hydroxyalkyl group (e.g. a hydroxyethyl group, and the like), or an allyl group; R

*Nano meter (minus 9 power of 1 meter).

represents a hydrogen atom or a methyl group; Z represents an atomic group necessary to complete a 2-quinoline nucleus, a benzothiazole nucleus, a benzoselenazole nucleus, or a naphthothiazole nucleus, and the hydrogen atom of each of said nuclei may have been substituted; X represents an acid anion; and p is an integer of 1 or 2, said p being 1 when said R and R is a substituted alkyl group and said dye forms an intromolecular salt forming a betaine structure;

GENERAL FORMULA II Y1 Y2 O oH=ocH= W (Xi-n1 wherein R represents an ethyl group, an n-propyl group, an n-butyl group, or an allyl group; R represents a sulfopropyl group, a 'y-sulfobutyl group, a fi-sulfobutyl group, a fl-carboxybutyl group, or a w-carboxypentyl group; Y and Y each represent a sulfur atom or a selenium atom; X; represents an acid anion; and q is an integer of 1 or 2, said q being 1 when the dye takes a betaine structure; and

GENERAL FORMULA III Y3 Y4 Ilts CH=o-0H= v )3 l? 1? (X3'):1 Re R1 wherein R and R each represent a 'y-sulfopropyl group, a 'y -sulfobutyl group, a fi-sulfobutyl group, a B-carboxybutyl group, or a w-carboxypentyl group; R represents a methyl group or an ethyl group; Y and Y each represent a sulfur atom or a selenium atom; V and V each represent a halogen atom or a hydrogen atom; Xyrepresents an acid anion; and r is an integer of 1 or 2, said r is 1 when the dye takes a betaine structure.

As the acid anion employed above, there are illustrated a chlorine ion, a bromine ion, an iodine ion, a perchlorate ion, a p-toluenesulfonate ion, a benzenesulfonate ion, an ethylsulfate ion, and a methylsulfate ion.

DETAILED DESCRIPTION OF THE INVENTION It is particularly desirable for achievement of the above-mentioned objects that said monomethine cyanine dyes of the General Formula I be a combination of dyes shown by the following General Formula Ia with Ib:

GENERAL FORMULA Ia s CH I A R; l

GENERAL FORMULA 11) General Formula II or the General Formula III, and particularly together with the carbocyanine dye of the General Formula II. The dye of the General Formula I also is characterized in that it reduces less the red sensitivity of the J-aggregate formed by the dye of the General Formula II.

The sensitizing dye represented by the General Formula. II has such a structural feature that the dye is a carbocyanine dye having the specific N-substituent R or R and also has substituted thereto, a methyl group at the meso position thus giving the maximum sensitivity near about 650 nm. This results in providing the excellent feature of forming the stable J-aggregate which is damaged less by other dyes used together, an antifoggant, a stabilizer, etc., in comparison with the properties of a general carbocyanine dye having a methyl group at the meso position. In spite of these merits, the combination of the dyes of the General Formula I with II causes the tone reproduction to deteriorate as the J-band falls too sharp at longer wavelengths. This fault improved by employing together, the carbocyanine dye represented by General Formula III, and also by employing the dye of General Formula III together. When this is done, the white-light sensitivity of the emulsion can be increased without reducing the J-band by the carbocyanine dye represented by the General Formula II. Another feature of the carbocyanine dye represented by the General Formula III is that both N-substituents are alkyl groups having each a sulfone group or a carboxyl group, whereby harmful action during development is prevented and the high sensitivity and the granularity of the image are reduced.

The sensitizing dyes represented by the General Formulae I, II and III used in this invention may be prepared by known processes.

For instance, they may be easily produced by referring to the specifications of US. Pat. No. 2,503,776; German Pat. No. 929,080 and German Pat. No. 1,072,765.

Examples of the sensitizing dyes applicable to this invention are shown below, although the invention is not limited to these alone.

K/\ 7 CHJ 1 barn N/ t'h OF Ni CH- C i2H5 J-2H5 1- CH t C 3 ZM F (I-h) S CH: CH3 C2 4 Kl -on= Ni/ b (EH3 N II S S CH=C-OH\ 0 115 B!" (CH-8400 OH (II-b) S S J /CH CCH\ r l C2H5 CHgCH2?E-SO3 (II-c) S S 3 CH=G-CH I T 2 zM a l I z s M 3 The sensitizing dyes of this invention are dissolved in aqueous solutions or a water-miscible organic solvent (e.g., methanol, ethanol, acetone, methyl Cellosolve, and pyridine) and incorporated in a silver halide emulsion separately or as a mixture. Ultrasonic Waves may be applied to the system for stirring and accelerating the resolution of the dyes. In accordance with the manner for producing light-sensitive materials the amounts of the sensitizing dyes, the order of adding them, and the manner of adding them may be properly changed by those skilled in the art. The amount of the sensitim'ng dyes to be incorporated in the silver halide emulsion is preferably from 1 10- mole to 5 10- mole per mole of silver halide contained in the silver halide emulsion. The ratio by mole of the sensitizing dyes (II) to (III) to be incorporated in combination in the silver halide emulsion is preferably from 11% to 1:3 and the ratio by mole of the sensitizing dyes (II) to (I) is preferably from to 1:5.

As the silver halide emulsion used in this invention, there are silver iodobromide emulsion, a silver iodochlorobromide emulsion, and a silver chlorobromide emulsion. For Obtaining a high sensitivity, it is preferable to use a silver iodobromide emulsion sensitized chemically by a were added to the silver halide emulsion with stirring in a methanol solution thereof, after adding thereto 0.4 g. of a stabilizer, -methyl-7-oxy-1,3,4-trizazindridine as a methanol solution thereof and a surface active agent for coating, the silver halide emulsion thus prepared was sulfur sensitization, a reduction sensitlzation, or a noble coated onto a film and dried to give a light-sensitive mametal salt sensitization, or a combination of them. Also, terial. an antifoggant, a stabilizer, a sensitizer, a surface active The sample film was cut mto pieces and the sample agent, a hardening agent, a plasticizer, etc., may be added film was Wedge exposed to a light Source of a (10101 to the silver halide emulsion containing the sensitizing 10 perature of 2666 through a YF filte? dyes of this invention. Further, other water-soluble poly- Ted filter by the 1} Fllm w mers may be used in place of gelatin. Also, other photoby means sensltqmeter havlng a hght source graphic dyes may be used. The Silver halide emulsion is verted by using a Davls-Glbson filter to a color temperacoated on a proper support, such as a cellulose derivative ture of 5400 Another samRle thus f was film, polyethylene terephthalate film, a polycarbonate film, 15 Posed y means of 3 lfP dlfiffictlon gratmg Spectro' a baryta-coated paper, a resin-coated paper, a synthetic Photograph made by Namml Shokah paper and glass Sheet The samples exposed were then developed for 7 mm- The present invention will be better understood from Utes. at 200 R a developmg solunon havmg the the following examples, which are merely illustrative and lowmg composmon not limitative of the present invention: COMPOSITION FOR THE DEVELOPING SOLUTION EXAMPLE G. N-methyl-p-aminophenol sulfate 2 One kilogram of a silver iodobromide emulsion con- H d i 5.0 taining 6 mole percent of iodine was melted in a vessel Sodium sulfite 100 by heating. While maintaining the silver halide emulsion Borax 2,0 at C., the prescribed amounts of the sensitizing dyes Water added to make 1 liter.

TABLE 1 Dye 0! General. Dye 01 General Dye of General Relative spectral Formula I Formula II Formula III sensitivity Used amt. Used amt. Used amt. No; Comp. XlO- mole Comp. X10 mole Comp. XlO- mole Sy Sr (nm.)

1 Ia s 100 53s H0 8 600 170 630 Ia 1 He 6 680 170 630 111d 8 400 200 662 P x 1 I10 6 HM 0.25 700 200 632 }IIG 6 11111 0.25 730 240 632 2 I0 2 Ila 6 600 180 628 M 1110 s 680 200 650 I0 2 11a 6 IIIc 0.3 760 200 632 3 1} }IIb 6 650 160 628 IIIb 8 650 180 a 1}}11 6 HR) 0.3 730 180 630 4 Ig s e 680 :..'.:.::::3:::::..'.;. 11d 8 ...z .4 450 636 Ig 2 11d 6 560 160 634 V IIIa 8 600 180 650 Ig 2 11d 6 1H2 0.26 750 180 636 5 I-d 1 111-0 660 630 I-d 1 11-0 680 200 632 6- .:;."..:.:.:...:.:...::.s A 450 130 630 Ig 2 A 450 130 628 e 650 650 Ig 2 A 450 110 628 7. lo 2 I19. 600 200 630 I0 2 I113 550 180 628 e 360 180 650 Ie 2 I12. 500 140 626 s Ig 2 Ed 530 299 632 Ig 2 H11 560 160 634 r 380 200 660 Ig 2 I16. 400 140 634 9.-...:-."--; He 5 III: 0.3 670 632 lb 8 100 530 In 1 Ho 5 IIIe 0.3 700 200 632 10 Ii 8 80 540 Ii 1 He 5 Inc 0.3 680 200 632 11 Ia 1 He 5 I110 0.3 710 210 632 Ig 1 1 He 5 HR: 0.3 700 200 634 g }IIc 5 1116 0.3 730 220 634 From the strips obtained, the density was measured by using an S-type densitometer made by Fuji Photo Film Co., Ltd; the yellow filter sensitivity (S the red filter sensitivity (8,), and the maximum sensitivity Wavelength (A were determined as relative values. The standard point of the optical density to determine the sensitivities was a point of fog-+0.1. The results are shown in Table 1.

From the foregoing results, the merits of the present invention, as mentioned before, will be readily apparent to those skilled in the art.

Although the present invention has been adequately described in the foregoing specification and examples included therein, it is readily apparent that various changes and modifications may be made without departing from the scope and spirit thereof.

What is claimed is:

1. A silver halide photographic emulsion spectrally sensitized with a combination of at least one monomethine cyanine dye represented by General Formula I:

GENERAL FORMULA I wherein R and R each represent a member selected from the group consisting of an alkyl group, a substituted alkyl group selected from the group consisting of an acetoXyalkyl group, a sulfoalkyl group and a hydroxyalkyl group and an allyl group; R represents a member selected from the group consisting of a hydrogen atom and a methyl group; Z represents atomic group necessary to complete a member selected from the group consisting of a Z-quinoline nucleus, a benzothiazole nucleus, a benzoselenazole nucleus, and a naphthothiazole nucleus, the hydrogen atom of said nucleus capable of being substituted; X,- represents an acid anion; and p is an integer of l to 2; and p being 1 when said R or R is a substituted alkyl group and the dye takes a betaine structure; at least one of the carbocyanine dyes represented by General Formula II:

GENERAL FORMULA I1 wherein R represents a member selected from the group consisting of an ethyl group, an n-propyl group, an n-butyl group, and an allyl group; R represents a member selected from the group consisting of a y-sulfopropyl group, a 'y-sulfobutyl group, a e-sulfobutyl group, a 6-carboxybutyl group, and a w-carboxypentyl group; Y and Y each represent a member selected from the group consisting of a sulfur atom and a selenium atom; X represents an acid anion; and q is an integer of l or 2, said q is 1 when the dye takes a betaine structure, and at least one carbocyanine dye represented by General Formula III:

GENERAL FORMULA III wherein R and R each represent a member selected from the group consisting of a 'y-sulfopropyl group, a 'y-sulfobutyl group, a e-sulfobutyl group, a 6-carboxybutyl group, and a w-carboxypentyl group; R represents a member selected from the group consisting of a methyl group and an ethyl group; Y and Y each represents a member selected from the group consisting of a sulfur atom and a selenium atom; V and V each represent a member selected from the group consisting of a hydrogen atom and a halogen atom: X; represents an acid anion; and r is an integer of 1 or 2; said r being 1 when the dye takes a betaine structure.

2. A silver halide photographic emulsion spectrally sensitized with a combination of at least one monomethine cyanine dye represented by General Formula I:

GENERAL FORMULA I wherein R R R X and p each have the same defini tions as those of General Formula I of claim 1, at least one carbocyanine dye represented by General Formula 11:

GENERAL FORMULA H 2H: 5 wherein Y Y R X and q each have the same definitions as those of General Formula II of claim 1, and at least one carbocyanine dye represented by General Formula II:

wherein R R X and r each have the same definitions as those of General Formula III in claim 1.

3. A silver halide photographic emulsion spectrally sensitized with a combination of at least one of the monomethine cyanine dyes represented by General Formulas Ia or Ib:

GENERAL FORMULA Ia Ra S fill r ii N/ wherein R R R X and p each have the same definitions as those of General Formula I of claim 1; at least one of the carbocyanine dyes represented by the General Formula II:

11 GENERAL FORMULA 11 wherein R X and q each have the same definitions as those of General Formula H of claim 1, and a carbocyanine dye represented by the following formula:

4. The silver halide photographic emulsion of claim 1 wherein the substituted alkyl group of R and R is a member selected from the group consisting of an acetoxyalkyl group, a sulfoalkyl group and a hydroxy alkyl group.

5. The silver halide photographic emulsion of claim 1, wherein the amount of the sensitizing dye represented by the General Formulas I, II and III ranges from 1X10" moles to 5X10- moles per mole of the silver halide.

6. The silver halide photographic emulsion of claim 1, wherein the mole ratio of the sensitizing dyes (II) to (III) is 1: 1; to 1:3 and the mole ratio of the sensitizing dyes (II) to (I) is 19,5 to 1:5.

7. A photographic light-sensitive element comprising a layer containing the silver halide photographic emulsion of claim 1.

8. The silver halide photographic emulsion of claim 2 wherein the substituted alkyl group of R and R is a. member of the group consisting of an acetoxyalkyl group, a sulfoalkyl group and a hydroxyalkyl group.

9. The silver halide photographic emulsion of claim 2, wherein the amount of the sensitizing dyes represented by the General Formulas I, II and III ranges from 1X 10- mol to 10- mol pe mol of the silver halide.

10. The silver halide photographic emulsion of claim 2, wherein the mol ratio of the sensitizing dyes (II) (III) is 1: /s to 1:3 and the mol ratio of the sensitizing dyes (II) to (I) is 1: to 1:5.

11. The silver halide photographic emulsion of claim 1, wherein the dye of Formula I is a member selected from the group consisting of 12. The silver halide photographic emulsion of claim 1, wherein the dye of Formula II is a member selected from the group consisting of:

Se H Se S Se In a E 3 -'CH=CCH= --CH= CH= e l? (JJHzkSO'a (CHMSOFHKNCQHM Ca s (C 2)4 a" S S 2 5 13. The silver halide photographic emulsion of claim 1, CH=GC H: wherein the dye of Formula 111 is a member selected 01 N 01 from the group consisting of: N

(JJHQ-GEL-SOy- (CH (|3H-G OaNa Se Se H3 CH5 CH3 R f CT 1 l e erences n e UNITED STATES PATENTS N 2,430,072 11/1947 Nicholson et al. 96-424 (ozmisor JH MSO -HltHC HQ 0 3,348,949 10/1967 Bannert et al 96124 3,463,640 8/ 1969 Ficken et al. 96124 3,527,641 9/1970 Nakazawa et al. 96124 3,615,609 10/1971 Fry et al. 96124 Se Se CH5 I) J. TRAVIS BROWN, Primary Examiner N US. Cl. X.R.

hfimcoo- 12119410011 131, 137

UNITED STATES RATENT OFFICE CERTIFHIATE 0F (ZORRECTION Patent No.3, 74 01 Dated July 10, 1973 InVentOI(S) YOSHIYUKI NAKAZAWA ET AL It is certified that. error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

In the Heading The claim to Priority was omitted. Should read:-

@OIIQDDOQGICODOQQBOGOJ P IOOOIOI'ODIOZSlTl/ Signed and sealed this 20th day of November- 1973.

(SEAL) Attesti EDWARD M.FLETGhER,JR. RENE D. 'I'EGTNEYER Attesting Officer Acting Commissioner of Patents ORM PO-1050 (10-69) USCOMM-DC 60376-1 69 us, covsnumzm PRINTING OFFICE was 0-356-354, 

